In Situ and Dump Leaching of Phosphate Rock Ind. Eng. Chem. Res. 1988,27, 2165-2169 2165 Fathi Habashi* and Farouk T. Awadalla Department of Mining & Metallurgy, Lava1 University, Quebec City, Canada GlK 7P4 Phosphate deposits with low carbonate content can be leached in situ or in dumps by dilute HC1 or HNO, to get a solution of monocalcium phosphate (eq 1). The acid concentration is critical: values higher than 10% HC1 and 20% HNO, cause blocking of the bed because of the formation of insoluble dicalcium phosphate and values lower than these cause the recovery to be low. P206 values can be recovered from the leach solution by crystallization of the double salt CaXH2P04.H20, where X = C1 or NO,; this can be decomposed at 200-250 "C to form dicalcium phosphate (eq 4 and 5). In this step, about 40% of the acid required for the leaching step can be recovered for recycle; the remainder can be regenerated by reacting the mother liquor with H2SO4 (eq 6 and 7). Radium can be separated from solution before the crystallization step so that nonradioactive gypsum can be obtained. Phosphate rock can be divided into two types: sedimentary and igneous deposits. Each of these in turn can be divided into two types: those containing significant amounts of carbonates and those containing minor amounts of carbonates (Lawver et al., 1978). Deposits of the latter type are widespread, for example, in Central Florida, Tennessee, Western USA, North Africa, and Kola Peninsula. Central Florida is one of the largest phosphate producers in the world; a typical deposit is shown in Figure 1 (anonymous, 1983). The mineralogical analysis of these deposits is approximately 28% calcium phosphate (Cas- (PO,),, bone phosphate of lime), 36% silica sand @ioz), and 34% clay minerals. To get 1 ton of a commercial product, 4.2 tons of overburden must be removed to expose 3.36 tons of ore, which is processed by physical and mechanical means to get the concentrate (1 ton), 1.4 tons of tailings, and 0.95 tons of slime waste (clays) as summarized in Figure 2 (Lawver et al., 1978, 1984). The problems facing this technology are as follows (anonymous, 1975; Balazik, 1983; Scheiner et al., 1982; White et al., 1975; Raulerson and Williams, 1983): (1) enormous material handling (6.55 tons of waste/ton of product) over long distances which is done by pumping the material as water slurry; (2) enormous long time for the slime waste to settle (years) in ponds prepared for this purpose (hence large areas and huge quantities of water are tied in this circuit), and (3) revegetation of the overburden and tailings piles, mandatory for protection of the environment and land reclamation. A large part of the product obtained is exported and the remainder is treated in Florida with H2S04 to produce H3P04 for making ammonium phosphate fertilizer. Another problem of this processing is the production of large amounts of gypsum-containing radium, the decay product of uranium, originally present in the rock. Each ton of phosphate rock treated by H2S04 produces 1.5 tons of gypsum, which represents an additional disposal and land problem. The purpose of the present work was to introduce to the phosphate industry a technology widely used in the hydrometallurgy of nonferrous metals, namely, in situ and dump leaching (Habashi, 1969; Schlitt and Hiskey, 1981; Schlitt, 1979,1985; anonymous, 1981; Hiskey, 1984; Dahl, 1985). Applying in situ leaching technology, also known as solution mining, to extract phosphate values from the deposit without transportation of the rock and to find ways to recover these values from solution as a concentrate suitable for shipping to processing plants or for export is new to the phosphate industry. In situ leaching, however, is used extensively for recovering copper, uranium, potash, and other salts. In one system of this technology, the 0888-5885/88/2627-2165$01.50/0 leaching agent is injected into the deposit, and the solution containing the solubilized minerals is pumped to the surface through special collecting holes drilled for the purpose of recovering the values and recycling the solution after adjusting its composition. Figure 3 shows a typical in situ leaching operation actually used in the uranium industry. A similar technology is used for extracting sulfur from underground by the Frasch process since the beginning of this century, and extensive testing has been carried out recently for the recovery of coal by underground gasification. When treating phosphate rock in situ, it will not be possible to use the common and the cheapest acid, H2S04, because gypsum formed during leaching will block its passage. Therefore, the more expensive acids HC1 and HNO, must be used. These acids, although expensive, have the advantage of solubilizing rapidly not only P205 content of the rock but also the uranium, the lanthanides, and the radium present; hence, their recovery or disposal (in the case of radium) can be conducted. In case of H2S04 leaching in conventional plants, only uranium can be recovered because the lanthanides and radium are retained in the gypsum (Hignett, 1985). Uranium in the rock is about 0.015% and the lanthanides about 0.5%. Considering the large tonnage of rock treated and the ease with which these metals can be recovered without interfering with the production of the fertilizers, it becomes evident that the rock treated in this way represents an important source for these metals. Beside the expensive acids HC1 and HNO,, it may also be possible to use sulfurous acid for in situ leaching of phosphate rock. This acid is obtained by dissolving SOz in water-a gas that may be a waste product of the nonferrous metal industry. There are also circumstances when it is desired to leach mined phosphate ore or a phosphate impurity from certain metallic ores, for example, pyrochlore, ilmenite, etc. In this case, the dump leaching technology may be used; i.e., a terrain is prepared on which the crushed ore is piled and the leaching acid is introduced at the top of the pile and collected at the bottom-a system that is also extensively used for gold, copper, and uranium ores (Habashi, 1969). In the present work, experiments were conducted to explore this possibility and to find methods for recovering the phosphate values as a high-grade concentrate suitable for shipment to the processing plant or for export. Experimental Section Materials. Phosphate rock sample was obtained from central Florida analyzing 18.22% Pz05, which corresponds to 40% calcium phosphate and 60% insoluble gangue 0 1988 American Chemical Society